Modelling and experimental study of separators for co-solvent recovery in a supercritical extraction process

Co-solvent recovery in supercritical extraction is addressed here through a theoretical description of the behaviour of a CO2 + co-solvent mixture into a cascade of cyclonic separators, such as those existing in conventional fractionation processes based on depressurisation cascades. Conversely to the conventional simplified approach that considers a separator as a plain theoretical stage, our study proposes a dynamic modelling that accounts for the probable droplet entrainment by the light phase and the re-vaporisation phenomenon after the valve. Fractionation experiments of CO2 + n-propyl alcohol mixtures were operated in a three-stage fractionation pilot, and experimental results are compared with simulation ones. The study demonstrates the relevance of our modelling, and points out the importance of entrainment effects, especially for low-pressure operated separators

Fluid phase equilibria of the reacting mixture in the dimethyl carbonate synthesis from supercritical CO2

In order to investigate the dimethyl carbonate synthesis from methanol and supercritical CO2, the thermodynamic behaviour of the reacting mixture, i.e. the quaternary methanol/CO2/DMC/water mixture, has to be known. The SRK equation of state with MHV2 mixing rules has been chosen to predict fluid phase equilibria in the reactor. The first part of this work is dedicated to the determination of binary interaction parameters, needed in the use of this model. These parameters are deduced from the fitting of experimental data concerning binary or ternary sub-systems existing in the quaternary mixture. Literature data was used for most of the binary sub-systems, but for the DMC/CO2 and DMC/water mixtures, specific experiments were carried out. The agreement between experimental and predicted fluid phase equilibria was found to be satisfactory. With a view to studying of the operating conditions for the reaction, the thermodynamic model was used to predict fluid phase equilibria in the reactor, by considering several hypothetical feed ratios and conversions. This work shows that CO2 has to be used in large excess in order to be sure of running the reaction in a homogeneous fluid medium

Experimental study of high pressure phase equilibrium of (CO2 + NO2/N2O4) mixtures

Experimental bubble pressure, as well as liquid density of (CO2 + NO2/N2O4) mixtures are reported at temperatures ranging from (298 to 328.45) K. Experiments were carried out using a SITEC high-pressure variable volume cell. Transition pressures were obtained by the synthetic method and liquid density was deduced from measurement of the cell volume. Correlation of experimental results was carried out without considering chemical equilibrium of NO2/N2O4 system. (Liquid + vapour) equilibrium was found to be accurately modelled using the Peng–Robinson equation of state with classical quadratic mixing rules and with a binary interaction coefficient kij equal to zero. Nevertheless, modelling of liquid density values was unsatisfactory with this approach

Carbon Dioxide, a Solvent and Synthon for Green Chemistry

Carbon dioxide is a renewable resource of carbon when we consider the reuse of existing CO2 as a carbon source for producing chemicals. The development of new applications is of major interest from the point of view of carbon dioxide sequestration and within the scope of green chemistry. For example, using CO2 instead of CO or COCl2 for chemical synthesis constitutes an attractive alternative avoiding hazardous and toxic reactants. However, it has the lowest chemical reactivity, which is a serious drawback for its transformation. Supercritical CO2 as a reaction medium offers the opportunity to replace conventional organic solvents. Its benign nature, easy handling and availability, non volatile emitting, and the relatively low critical point (Pc = 73.8 bar, Tc = 31 °C) are particularly interesting for catalytic applications in chemical synthesis, over a wide range of temperatures and pressures. The benefits of coupling catalysis and supercritical fluids are both environmental and commercial: less waste and VOCs emission, improved separation and recycling, and enhanced productivity and selectivity. The case study described in this paper concerns the reaction of carbon dioxide with alcohols to afford dialkyl carbonates with special emphasis on dimethyl carbonate. It is of significant interest because the industrial production of this class of compounds, including polycarbonates, carbamates, and polyurethanes, involves phosgene with strong concerns on environmental impact, transport, safety and waste elimination. The future of carbon dioxide in green chemistry, including supercritical applications, is highly linked to the development of basic knowledge, know-how, and tools for the design of catalyst precursors and reactors

Cellulosic materials as biopolymers and supercritical CO2as a green process: chemistry and applications

In this review, we describe the use of supercritical CO2 (scCO2) in several cellulose applications. The focus is on different technologies that either exist or are expected to emerge in the near future. The applications are wide from the extraction of hazardous wastes to the cleaning and reuse of paper or production of glucose. To put this topic in context, cellulose chemistry and its interactions with scCO2 are described. The aim of this study was to discuss the new emerging technologies and trends concerning cellulosic materials processed in scCO2 such as cellulose drying to obtain aerogels, foams and other microporous materials, impregnation of cellulose, extraction of highly valuable compounds from plants and metallic residues from treated wood. Especially, in the bio-fuel production field, we address the pre-treatment of cellulose in scCO2 to improve fermentation to ethanol by cellulase enzymes. Other reactions of cellulosic materials such as organic inorganic composites fabrication and de-polymerisation have been considered. Cellulose treatment by scCO2 has been discussed as well. Finally, other applications like deacidification of paper and cellulosic membranes fabrication in scCO2 have been reviewed. Examples of the discussed technologies are included as well

SFGP 2007 - Investigation of a Novel Principle of Chemical Grafting for Modification of Cellulose Fibers

Natural cellulose fibres have been employed for packaging applications for a long time. Their use, however, has been hampered by their high hydrophilicity and their moisture sensitivity. It has, thus, been proposed to circumvent this problem through the hydrophobic modification of their surface thanks to the use of molecular grafting approaches. In this work, we describe the use of a novel solvent-free chemical pathway for molecular grafting that we have coined chromatogenic chemistry. It involves a reaction between a solid substrate and a reagent which is in a vapour-liquid equilibrium and diffuses within the solid substrate through a mechanism of adsorption/desorption akin to gas chromatography. Chromatogenic chemistry phenomenon has been studied and modelled through the extensive use of a new specific test, the Droplet Surface Migration Test. It involves the deposition upon a porous substrate of a small amount of reagent and in studying its subsequent migration and grafting. Whatman paper and various long chain acid chlorides were used for this modelling. The acid chloride carboxylic ends react with the external hydroxyl groups of cellulose fibres to give rise to the formation of long chain hydrophobic ester bonds. Upon immersion of the paper sheet in distilled water, a hydrophobic spot, extending well over the initial depot zone, could then be clearly visualized, allowing to follow conveniently the reagent migration and reaction. Grafting densities were performed by using the HPLC technique. The results obtained through the use of this test allowed a better understanding of chromatogenic chemistry phenomenon and an identification of the main parameters which affect the process: the nature of the reagent, the temperature, the reaction time, the nature of the substrate, etc. We have more particularly shown that the diffusion and grafting yields were maximal for a specific temperature which increases with the boiling point and therefore with the chain length of the reagents. We have proposed that this temperature should correspond to a compromise between the diffusion and reactivity properties of the reagent, its evaporation and its degradation by hydrolysis

Electrochemical determination of ferrocene diffusion coefficient in liquid media under high CO2 pressure: Application to DMF–CO2 mixtures

Electrochemical method can be useful for the determination of diffusion coefficients in various media. For low polarity media, ultramicroelectrodes are preferably used. In this work, the electro-oxidation of ferrocene has been studied in dimethylformamide (DMF)–CO2 mixtures under various CO2 pressures, using a 100 lm diameter Pt microelectrode. Tetrabutylammonium perchlorate (TBAP) was chosen as the supporting electrolyte. Cyclic voltammetry was used in order to obtain values of diffusion coefficient of ferrocene, which were determined by using the Randles–Sevcik relation. This method proved to be convenient in such low polarity solvent. In addition, fluid phase equilibria of CO2–DMF mixtures were calculated and pressure–composition phases diagrams were established for the concerned binary mixtures, thanks to commercial Prophy PlusTM software (Prosim S.A., France). So, both liquid phase expansion, due to swelling by high-pressure CO2 and effective bulk concentration of ferrocene were estimated. Nevertheless, electrochemical measurements were problematic when high-pressure single phase conditions of CO2–DMF mixtures were reached

Electrocarboxylation in supercritical CO2 and CO2-expanded liquids

In this study, the electrocarboxylation of benzyl chloride in pressurized CO2, or pressurized mixtures of dimethylformamide (DMF) and CO2, was investigated in order to synthesize phenylacetic acid. A stainless steel cathode was used as the working electrode, whereas a sacrificial massive magnesium rod or a platinized platinum grid was used as the anode, tetrabutylammonium perchlorate (TBAP) or tetrakis(decyl)ammonium tetraphenylborate (TDATPhB) being the supporting electrolyte. The electrocarboxylation was carried out at 40 ◦C, at operating pressures of 1, 6, 7, 8, 9 and 12MPa, using current densities ranging from 0.1 to 150mAcm−2. It was found that a small amount of DMF was necessary to ensure the solubility of the supporting electrolyte, to obtain sufficient electrical conductivity of the medium. The best resultswere obtained using the magnesium sacrificial anode, at 6MPa. After consumption of the theoretical amount of electrical current (2F mol−1), 65.7% benzyl chloride conversion was reached, together with an 82.4% phenylacetic acid selectivity and a 54.2% faradaic yield. Detected by-productswere toluene, bibenzyle, benzyl alcohol and benzaldehyde

Optimizing the process of supercritical extraction of lemon balm (Melissa Officinalis L.)

This work investigates the process of extraction of lemon balm (Melissa officinalis L.) by treatment with carbon dioxide at supercritical conditions. The process kinetics is studied at different operational conditions, and the influence of some important regime parameters (pressure, temperature particle size, solvent flow-rate) on the extraction yield is experimentally determined. Besides the information for process intensity at particular operational regimes, the results are useful for selection of favourable operational conditions for better extraction, i.e. for production of larger quantity of extracted substances from unit mass of raw material

Phase equilibrium of the CO2/glycerol system: Experimental data by in situ FT-IR spectroscopy and thermodynamic modeling

Phase equilibrium experimental data for the CO2/glycerol system are reported in this paper. The measurements were performed using an in situ FT-IR method for temperatures ranging from 40 ◦C to 200 ◦C and pressures up to 35.0 MPa, allowing determination of the mutual solubility of both compounds. Concerning the CO2 rich phase, it was observed that the glycerol solubility in CO2 was extremely low (in the range of 10−5 in mole fraction) in the pressure and temperature domains investigated here. Conversely, the glycerol rich phase dissolved CO2 at mole fractions up to 0.13. Negligible swelling of the glycerol rich phase has been observed. Modeling of the phase equilibrium has been performed using the Peng–Robinson equation of state (PR EoS) with classical van der Waals one fluid and EoS/GE based mixing rules (PSRK and MHV2). Satisfactory agreement was observed between modeling results and experimental measurements when PSRK mixing rules are used in combination with UNIQUAC model, although UNIFAC predictive approach gives unsatisfactory representation of experimental behavior